CN102027349A - Quartz oscillator and measurement method using same - Google Patents

Quartz oscillator and measurement method using same Download PDF

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Publication number
CN102027349A
CN102027349A CN2009801172657A CN200980117265A CN102027349A CN 102027349 A CN102027349 A CN 102027349A CN 2009801172657 A CN2009801172657 A CN 2009801172657A CN 200980117265 A CN200980117265 A CN 200980117265A CN 102027349 A CN102027349 A CN 102027349A
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quartz crystal
crystal unit
frequency
electrode
value
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市桥素子
伊藤敦
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Ulvac Inc
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Ulvac Inc
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N11/00—Investigating flow properties of materials, e.g. viscosity, plasticity; Analysing materials by determining flow properties
    • G01N11/10—Investigating flow properties of materials, e.g. viscosity, plasticity; Analysing materials by determining flow properties by moving a body within the material
    • G01N11/16—Investigating flow properties of materials, e.g. viscosity, plasticity; Analysing materials by determining flow properties by moving a body within the material by measuring damping effect upon oscillatory body
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N29/00—Investigating or analysing materials by the use of ultrasonic, sonic or infrasonic waves; Visualisation of the interior of objects by transmitting ultrasonic or sonic waves through the object
    • G01N29/02—Analysing fluids
    • G01N29/022—Fluid sensors based on microsensors, e.g. quartz crystal-microbalance [QCM], surface acoustic wave [SAW] devices, tuning forks, cantilevers, flexural plate wave [FPW] devices
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N29/00—Investigating or analysing materials by the use of ultrasonic, sonic or infrasonic waves; Visualisation of the interior of objects by transmitting ultrasonic or sonic waves through the object
    • G01N29/02—Analysing fluids
    • G01N29/036—Analysing fluids by measuring frequency or resonance of acoustic waves
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N29/00—Investigating or analysing materials by the use of ultrasonic, sonic or infrasonic waves; Visualisation of the interior of objects by transmitting ultrasonic or sonic waves through the object
    • G01N29/22—Details, e.g. general constructional or apparatus details
    • G01N29/24—Probes
    • G01N29/2437—Piezoelectric probes
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N9/00—Investigating density or specific gravity of materials; Analysing materials by determining density or specific gravity
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N9/00—Investigating density or specific gravity of materials; Analysing materials by determining density or specific gravity
    • G01N9/002—Investigating density or specific gravity of materials; Analysing materials by determining density or specific gravity using variation of the resonant frequency of an element vibrating in contact with the material submitted to analysis
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R1/00—Details of instruments or arrangements of the types included in groups G01R5/00 - G01R13/00 and G01R31/00
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2291/00—Indexing codes associated with group G01N29/00
    • G01N2291/02—Indexing codes associated with the analysed material
    • G01N2291/028—Material parameters
    • G01N2291/02818—Density, viscosity
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2291/00—Indexing codes associated with group G01N29/00
    • G01N2291/04—Wave modes and trajectories
    • G01N2291/042—Wave modes
    • G01N2291/0426—Bulk waves, e.g. quartz crystal microbalance, torsional waves

Abstract

Disclosed is a quartz oscillator, and a measurement method using the same, which make it possible to measure only the density of a solution, or to measure the density and viscosity simultaneously, by means of a quartz oscillator equipped with one detection unit. Electrodes are provided on both sides of a piezoelectric plate, a substance to be measured is brought into contact with a quartz oscillator in which an uneven surface is formed on the electrode or the detection unit of an electrode on the side that comes into contact with the substance to be measured, the quartz oscillator is caused to oscillate, and the density of the aforementioned substance is measured by measuring the amount of change in a frequency (f2) that corresponds to the high-frequency side of two frequencies that represent a value that is half of the maximum value of the conductance of the aforementioned quartz oscillator.

Description

Quartz crystal unit and the assay method that has used this quartz crystal unit
Technical field
The present invention relates to only to measure separately the density of solution or the assay method that can measure the quartz crystal unit of density and viscosity simultaneously and use this quartz crystal unit.
Background technology
QCM (Quartz CrystalMicrobalance for the resonance effect of having utilized quartz crystal unit, QCM (Quartz Crystal Microbalance)) method, as the method that can detect extremely small mass change by simple device, be not only gas phase but also can realize mensuration under the liquid phase, so by extensively with the interactional biology sensor etc. that is biosome materials such as gas sensor, film thickness sensor, chemical sensor, mensuration DNA/ protein.
In QCM method in the past, to the resonant frequency that obtains by vibration or by impedance analysis device, network analyser etc. frequency is scanned the resonant frequency that obtains and measure, thereby carry out various mensuration.
In the mensuration under the gas phase in QCM, owing to the quality that only will be attached to the material in the electrode surface is surveyed as frequency variation, so be easier to the ratio of transformation of density.
But, under the situation that the density and the viscosity of solution are measured, different with the situation of gas phase, resistance for the solution relevant with the vibration plane of quartz crystal unit, owing to frequency change with density and viscosity are carried out multiplication and calculate the value that obtains and have correlationship, so in QCM method in the past, be difficult to carry out the separation determination of the density and the viscosity of solution.
Therefore, be under the condition of unknown in density and this two side of viscosity, in QCM method in the past, can't obtain density and viscosity value separately.
With respect to this, shown in patent documentation 1, patent documentation 2, following method has been proposed: the test section more than 2 is set in sensor, with at least 1 test section with act on to the frequency of the resistance of solution measure with reference to using, from the measurement result of remaining test section, remove resistance, thereby density, the viscosity of solution are measured with reference to the solution of the sensor of usefulness.
But,, then exist the manufacturing cost of bothersome or sensor to increase, and produce the such problem of individual difference at each test section if a plurality of test sections are set in 1 piezoelectric board or use a plurality of sensors.
In addition, under the situation of the inspection amount line that draws by 1 sensor, need to prepare the sample of a plurality of standards, till the mensuration of reality, need such problem of time so exist, and then, only obtain density, viscosity, so there is the quite low such problem of precision of measuring according to the resonant frequency that comprises density and this two side's of viscosity information.
Patent documentation 1: No. 5741961 communique of United States Patent (USP)
Patent documentation 2: No. 5798452 communique of United States Patent (USP)
Summary of the invention
The assay method that the object of the present invention is to provide a kind of quartz crystal unit and used this quartz crystal unit by possessing the quartz crystal unit of 1 test section, can only be measured the density of solution separately or can measure density and viscosity simultaneously.
In order to solve described problem, the 1st aspect of the present invention provides a kind of assay method that uses quartz crystal unit, it is characterized in that, make the determination object thing touch quartz crystal unit and make quartz crystal unit vibration, wherein in this quartz crystal unit, in the two sides of piezoelectric board, possess electrode, formed male and fomale(M﹠F) in electrode that in a side of the material contact that becomes determination object, disposes or the test section on this electrode
To the frequency (f that is equivalent to high frequency side in peaked half 2 frequencies of value of the conductivity of representing described quartz crystal unit 2) variable quantity measure, thereby the density of described material is measured.
The 2nd aspect aspect the 1st in, it is characterized in that, the variable quantity of at least 2 frequencies of the frequency on the admittance circle line chart of described quartz crystal unit is measured, measure the viscosity of described material in the lump.
The 3rd aspect aspect the 1st in, it is characterized in that at least 2 frequencies on the described admittance circle line chart are peaked half 2 frequency (f of value of the conductivity of the described quartz crystal unit of expression 1, f 2) and the resonant frequency (f of described quartz crystal unit s) in any 2.
The 4th aspect aspect the 1st in, it is characterized in that, for described frequency (f 2), to the admittance circle line chart of described quartz crystal unit on the minimum value (B of susceptance Min) suitable frequency directly measures.
The 5th aspect aspect the 1st in, it is characterized in that, by peaked half 2 frequency (f of value the conductivity of representing described quartz crystal unit 1, f 2) between frequency in the variable quantity of at least 2 frequencies measure, measure the viscosity of described material in the lump.
The 6th aspect aspect the 5th in, it is characterized in that described at least 2 frequencies are peaked half 2 frequency (f of value of the conductivity of the described quartz crystal unit of expression 1, f 2) and the resonant frequency (f of described quartz crystal unit s) in any 2.
The 7th aspect aspect the 1st in, it is characterized in that, according to the frequency (f that is equivalent to lower frequency side in peaked half 2 frequencies of value of the conductivity of the described quartz crystal unit of expression 1) and resonant frequency (f s), measure described frequency (f indirectly 2).
The 8th aspect aspect the 1st in, it is characterized in that, measure by the basic frequency or the higher hamonic wave of described quartz crystal unit.
In addition, as quartz crystal unit of the present invention, the 9th aspect provides a kind of quartz crystal unit, it is characterized in that, in the two sides of piezoelectric board, possess electrode, in the electrode or the test section on this electrode that in a side of the material contact that becomes determination object, disposes, formed the male and fomale(M﹠F) that density measurement is used.
The 10th aspect aspect the 9th in, it is characterized in that described male and fomale(M﹠F) is that arithmetic mean thickness (Ra) is the face of 0.1 μ m～20 μ m.
The 11st aspect aspect the 9th in, it is characterized in that, described male and fomale(M﹠F) with a plurality of grooves in abutting connection with and constitute.
According to the present invention, what the QCM method by in the past of can realizing can't realize only measures the density of solution separately easily or measures density and viscosity simultaneously easily by the quartz crystal unit with 1 test section.
Description of drawings
Fig. 1 is the key diagram of admittance (admittance) circle diagram of quartz crystal unit.
Fig. 2 is the quartz crystal unit ((a) vertical view, (b) A-A ' sectional view, (c) B-B ' sectional view) that uses in one embodiment of the invention.
Fig. 3 is the stereographic map of groove that is used to illustrate the test section of this quartz crystal unit.
Fig. 4 is the key diagram that is illustrated in the apparatus structure that uses in the assay method of one embodiment of the present of invention.
Fig. 5 is the curve that has compared the density of the measurement result of density of present embodiment and chemical brief guide.
Fig. 6 is the curve that has compared the viscosity of the measurement result of viscosity of present embodiment and chemical brief guide.
(symbol description)
1: piezoelectric board; 2: gold electrode; 3: quartz crystal unit; 4: groove; 5: sensor; 6: the π circuit; 7: network analyser.
Embodiment
In the quartz crystal unit of Shi Yonging, in the two sides of piezoelectric board, possess electrode in the present invention, in electrode that in a side, disposes or the test section that on this electrode, forms, formed male and fomale(M﹠F) by evaporation or sputter as the contact of the material of determination object.
As the method that in the surface of described electrode surface or test section, forms male and fomale(M﹠F), for example, be pre-formed male and fomale(M﹠F) at the surface at the position of the test section that crystal slab is set or suppress crystal slab surface grinding degree and form metal film thereon as electrode.In addition, can also to described electrode surface or test section part male and fomale(M﹠F) is set.
Preferably described male and fomale(M﹠F) is made as the face that arithmetic mean thickness (Ra) is 0.1 μ m～20 μ m.It is former because if Ra less than 0.1 μ m, then can't measure the density of determination object thing, its result can't obtain viscosity.And if surpass 20 μ m, then quartz crystal unit can't be kept the state that is suitable for measuring, and measures frequency and might become unstable or can't obtain each frequency self.
In addition, described male and fomale(M﹠F) preferably is made as groove, and a plurality of these grooves preferably are set.Its purpose is to form the concave surface of accommodating the determination object thing.In addition, the width of this groove is preferably about 0.1～100 μ m, and its degree of depth is preferably about 0.1～40 μ m.In addition, crystal slab is owing to vibrate on certain direction abreast with the plate face, so in order in groove, to catch the determination object thing reliably, the outgoing direction that prolongs of groove can be made as the direction that intersects with the direction of vibration of crystal slab, preferably be made as the vertical direction of relative direction of vibration.
Next, use described quartz crystal unit, an embodiment of assay method of the present invention is described.
At first, make quartz crystal unit frequency vibration according to the rules, make the determination object thing touch electrode or be formed on test section on the electrode.
At this moment, to the frequency (f that is equivalent to high frequency side in peaked half 2 frequencies of value of the conductivity of expression quartz crystal unit 2) variable quantity measure, and the variable quantity of at least 2 frequencies existing on the admittance circle line chart of the characteristic of expression quartz crystal unit shown in Figure 1 is measured.
Provide the mass loading of the relative material of frequency variation of the point on this admittance circle line chart to present identical variable quantity, but the frequency variation that causes owing to the resistance of solution have the character that becomes different variable quantities under each frequency.
Therefore, for example, for because the frequency f that is equivalent to lower frequency side in peaked half the frequency of value of the conductivity of expression quartz crystal unit 1Solution resistance and the frequency variation that is subjected to is resonant frequency f s2 times of the frequency variation that is subjected to owing to the resistance of solution.On the other hand, for the frequency f that is equivalent to high frequency side in peaked half the frequency of value of the conductivity of expression quartz crystal unit 2The frequency variation that is subjected to owing to the resistance of solution does not almost have.
It can also be according to frequency f 1, f sAnd f 2Solution in following approximate expression understand.
[formula 1]
Δf 1 = - 2 N f 0 2 ρ Q μ Q Δm A - 2 N 1 / 2 f 0 3 / 2 ρ L η L π ρ Q μ Q · · · · ( 1 )
[formula 2]
Δf s = - 2 N f 0 2 ρ Q μ Q Δm A - N 1 / 2 f 0 3 / 2 ρ L η L π ρ Q μ Q · · · · ( 2 )
[formula 3]
Δf 2 = - 2 N f 0 2 ρ Q μ Q Δm A · · · · ( 3 )
In above-mentioned formula (1)～formula (3), f 0Expression basic frequency, N represent number of times (N=1,3,5...), the η of higher hamonic wave LExpression viscosity, ρ QDensity, the μ of expression quartz crystal unit QShearing elasticity coefficient, the Δ m of expression quartz crystal unit represent that mass change amount, A represent electrode area, ρ LDensity, the μ of expression solution LThe viscosity of expression solution.
According to such character, for example, if measure f in the lump 1, f 2, f s, f then 2Owing to be not subjected to the influence of the resistance of solution,, this frequency variation is taken into the quality of the determination object thing in the male and fomale(M﹠F) so representing the vibration of the electrode by quartz crystal unit.
So if obtain the volume that is taken into the liquid in this male and fomale(M﹠F) by measure waiting in advance, and the quality that through type (3) is obtained then can be obtained density divided by this volume.
On the other hand, in the frequency on the admittance circle line chart of quartz crystal unit, because the frequency variation that mass loading causes presents identical variation, so f sExcept being subjected to owing to the influence of the frequency variation that the resistance of solution causes, also be subjected to the influence of the frequency variation of described mass loading.f 1Similarly except being subjected to owing to the influence of the frequency variation that the resistance of solution causes, also be subjected to the influence of the frequency variation of described mass loading.
Therefore, by will be according to f 2The density obtained of frequency variation and only the frequency variation of the resistance of determination object thing be updated in the following formula (4), can obtain viscosities il L
[formula 4]
Δf L = Δ ( f 1 - f 2 ) 2 = - N f 0 3 / 2 ρ L η L π ρ Q μ Q · · · · ( 4 )
Δ f LThe frequency variation of representing the resistance of the only determination object thing relevant with the vibration plane of quartz crystal unit.
In addition, as described frequency (f 2), can directly measure minimum value (B with the susceptance (susceptance) of admittance circle line chart Min) suitable frequency or according to peaked half 2 frequencies of value of the conductivity of expression quartz crystal unit in the frequency (f that is equivalent to lower frequency side 1) and resonant frequency (f s) utilization (f 1+ f 2)/2=f sRelation measure indirectly.
In addition, for for the frequency variation of the resistance of obtaining the only determination object thing relevant and the frequency of measuring so long as at least 2 frequencies on the admittance circle line chart then are not particularly limited, is not limited to illustrated f with the vibration plane of quartz crystal unit 1And f 2, also can measure f 1And f s, or f sAnd f 2
In addition, the frequency of using in the mensuration is not limited to first-harmonic, as long as use each higher hamonic wave, then can be reduced in the pressure wave that produces between quartz crystal unit and the liquid level, can as the record of TOHKEMY 2005-98866 communique, measure by the solution of trace.
In addition, in the mensuration of described frequency, both can be to make quartz crystal unit vibration and carry out method for measuring by frequency counter, also can be to use impedance analysis device, network analyser to come the method for sweep frequency.
In addition,, can enumerate mounting type, sheath flow pattern of a glass type, drop etc., on form, be not particularly limited, and can measure density, the viscosity of solution for the shape of the sensor periphery that comprises sensor.
Embodiment
Next, with reference to accompanying drawing, one embodiment of the present of invention are described.
As shown in Figure 2, preparation possesses the quartz crystal unit 3 of the 27MHz of gold electrode 2,2 in the both sides of piezoelectric board 1, in the surface of the gold electrode 2 of a side of the solution of this quartz crystal unit 3 contact, as shown in Figure 3, adjacency a plurality of grooves 4,4,4 that its section is a rectangular shape are set, on electrode 3, have formed test section.
Electrode 2,2 gold by diameter 2.7mm constitute, and the groove width W of groove 4 and groove I at interval all are 5 μ m, and the depth D of groove is 600nm.
In the piece with the aluminium of automatic agitating function and tempering machine this quartz crystal unit 3 is set and as sensor 5, as shown in Figure 4, is connected to the network analyser 7 of measuring frequency by π circuit 6, the signal of automatic network analyzer 7 is taken in the PC 8 in the future.
In addition, sensor 5 is maintained 25 ℃ with the liquid temperature of determination object thing in following mensuration.
At first, on the electrode 4 of quartz crystal unit 3, be that the glycerine water solution of the 10wt%, the 30wt% that had both known and 50wt% is as measuring sample, the frequency when having measured mounting 500 μ l with benchmark sample (pure water) and density and viscosity.
Following table 1 illustrates f 2, in order to compare and according to the f of resonant frequency with in the past QCM method s, f 1, f 2(the f that obtains 1-f 2The variable quantity of)/2 frequency separately.
[table 1]
Glycerine (wt%) Δf 2 Δf s Δ(f 1-f 2)/2
0 (reference solution) -7070 -15855 -8795
10 -7347 -17418 -10079
30 -7620 -21412 -13792
50 -7953 -28697 -20780
Use pure water as the benchmark sample, and measuring f 2Frequency variation the time owing to be Δ f 2=-7070Hz, thus form in the test section on the electrode recessed in the amount of the solution that is taken into be 213pl.
In addition, be that 30pg/Hz, 25 ℃ the density of pure water are 0.997g/cm in the sensitivity of the quartz crystal unit 3 of 27MHz 3Condition under calculate.
For the f that in QCM method in the past, uses sOwing to survey the frequency that is detected as the quality that is taken in test section concavo-convex, with the aggregate value of the frequency of the resistance of solution, so can't obtain the amount that is taken into the solution that is detected as quality in concavo-convex according to the frequency variation that obtains by mensuration.
Because the amount of the solution that is detected out as quality that is taken in concavo-convex on electrode 4 is 213pl, so can be in view of the above calculate density according to the frequency variation of the glycerine water solution of described 10wt%, 30wt% and 50wt%.
Following table 2 and the curve of Fig. 5 illustrate its result.
[table 2]
Figure BPA00001255184700081
The value of the density of obtaining according to frequency variation illustrates the close value of density with chemical brief guide (distribution in 1984, the 3rd edition) record.
Next, according to (the f of the frequency of the resistance of density of obtaining from described frequency variation and the expression only solution relevant with the vibration plane of quartz crystal unit 3 1-f 2The frequency variation of)/2 has been obtained viscosity.
In addition, the density at quartz crystal unit 3 is 2.65g/cm 3, quartz crystal unit 3 the shearing elasticity coefficient be 2.95 * 10 11G/cmS 2Condition under calculate.
By each numerical value of substitution in formula (4), calculate viscosities il, so shown in the curve of following table 3 and Fig. 6.
[table 3]
Figure BPA00001255184700091
The value of the viscosity of obtaining according to frequency variation presents the close value of viscosity that calculates with value with reference to chemical brief guide.
In addition, for the viscosity that calculates with reference to the value of chemical brief guide, because the numerical value when not having 25 ℃, so be meant that value according to record before and after 25 ℃ is by the approximate value of obtaining.
More than, recognize density, the viscosity that can only measure simultaneously solution accurately by 1 quartz crystal unit 3 with 1 test section.
In addition, in described example, measure density and viscosity simultaneously, but can also only measure density individually.In addition, under the situation that only needs viscosity, can also only measure viscosity individually according to resulting density certainly.
Utilizability on the industry
The present invention can be used in and measure a small amount of liquid density and/or viscosity.

Claims (11)

1. an assay method that uses quartz crystal unit is characterized in that,
Make the determination object thing touch quartz crystal unit and make quartz crystal unit vibration, wherein in this quartz crystal unit, in the two sides of piezoelectric board, possess electrode, formed male and fomale(M﹠F) in electrode that in a side of the material contact that becomes determination object, disposes or the test section on this electrode
To the frequency f that is equivalent to high frequency side in peaked half 2 frequencies of value of the conductivity of representing described quartz crystal unit 2Variable quantity measure, thereby the density of described material is measured.
2. the assay method that uses quartz crystal unit according to claim 1 is characterized in that,
Variable quantity at least 2 frequencies of the frequency on the admittance circle line chart of described quartz crystal unit is measured, and measures the viscosity of described material in the lump.
3. the assay method that uses quartz crystal unit according to claim 2 is characterized in that,
At least 2 frequencies on the described admittance circle line chart are peaked half 2 frequency f of value of the conductivity of the described quartz crystal unit of expression 1, f 2And the resonant frequency f of described quartz crystal unit sIn any 2.
4. the assay method that uses quartz crystal unit according to claim 1 is characterized in that,
For described frequency f 2, to the admittance circle line chart of described quartz crystal unit on the minimum value B of susceptance MinSuitable frequency is directly measured.
5. the assay method that uses quartz crystal unit according to claim 1 is characterized in that,
By peaked half 2 frequency f of value to the conductivity of representing described quartz crystal unit 1, f 2Between frequency in the variable quantity of at least 2 frequencies measure, measure the viscosity of described material in the lump.
6. the assay method that uses quartz crystal unit according to claim 5 is characterized in that,
Described at least 2 frequencies are peaked half 2 frequency f of value of the conductivity of the described quartz crystal unit of expression 1, f 2And the resonant frequency f of described quartz crystal unit sIn any 2.
7. the assay method that uses quartz crystal unit according to claim 1 is characterized in that,
According to the frequency f that is equivalent to lower frequency side in peaked half 2 frequencies of value of the conductivity of the described quartz crystal unit of expression 1With resonant frequency f s, measure described frequency f indirectly 2
8. the assay method that uses quartz crystal unit according to claim 1 is characterized in that,
Basic frequency or higher hamonic wave by described quartz crystal unit are measured.
9. a quartz crystal unit is characterized in that,
In the two sides of piezoelectric board, possess electrode, in the electrode or the test section on this electrode that in a side of the material contact that becomes determination object, disposes, formed the male and fomale(M﹠F) that density measurement is used.
10. quartz crystal unit according to claim 9 is characterized in that,
Described male and fomale(M﹠F) is that arithmetic mean thickness Ra is the face of 0.1 μ m～20 μ m.
11. quartz crystal unit according to claim 9 is characterized in that,
Described male and fomale(M﹠F) constitutes a plurality of grooves adjacency.
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